Electrolytic copper process using anion permeable barrier

ABSTRACT

Processes and systems for electrolytically processing a microfeature workpiece with a first processing fluid and an anode are described. Microfeature workpieces are electrolytically processed using a first processing fluid, an anode, a second processing fluid, and an anion permeable barrier layer. The anion permeable barrier layer separates the first processing fluid from the second processing fluid while allowing certain anionic species to transfer between the two fluids. The described processes produce deposits over repeated plating cycles that exhibit resistivity values within desired ranges.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. application Ser. No.11/299,293, filed Dec. 8, 2005, which is a continuation-in-part of U.S.application Ser. No. 11/296,574, filed Dec. 7, 2005, priority from thefiling dates of which is hereby claimed under 35 U.S.C. §120.

FIELD OF THE INVENTION

The present invention relates to electrolytic processing of microfeatureworkpieces and an electrolytic treatment process that utilizes an anionpermeable barrier.

BACKGROUND OF THE INVENTION

Microfeature devices, such as semiconductor devices, imagers, displays,thin film heads, micromechanical components, microelectromechanicalsystems (MEMS), and large through-wafers vias are generally fabricatedon and/or in microfeature workpieces using a number of machines thatdeposit and/or etch materials from the workpieces. Many currentmicrofeature devices require interconnects and other very small,submicron sized features (e.g., 45-250 nanometers) formed by depositingmaterials into small trenches or holes. One particularly useful processfor depositing materials into small trenches and/or vias is electrolyticprocessing, e.g., electroplating. Typical electrolytic processingtechniques include electroplating processes that deposit copper, nickel,lead, gold, silver, tin, platinum, and other materials onto microfeatureworkpieces and etching processes that remove metals from microfeatureworkpiece surfaces.

In certain electroplating or etching processes, chelants or complexingagents are used to affect the electric potential at which metal ions aredeposited onto or removed from surfaces of microfeature workpieces.Other components that may be present in the processing fluids includeaccelerators, suppressors, and levelers which can affect the results ofthe electroplating or electroetching process. Although these types ofmaterials can positively influence the electroplating or electroetchingprocesses, their use is not without drawbacks. For example, it ispossible for these components to have an adverse impact on theelectrolytic process as a result of reactions or other interactions withelectrodes used in the electrolytic process.

Another challenge in depositing metals into narrow, deep trenches orvias is that it is difficult to completely fill the small featureswithout creating voids or other nonuniformities in the deposited metal.For example, when depositing metal into a trench having a criticaldimension of 45 nanometers to 250 nanometers, an ultrathin seed layermay be used, but care must be taken to ensure sufficient vacant space inthe trench for the subsequently deposited bulk metal. In addition,ultrathin seed layers may be problematic because the quality of thedeposited seed layer may not be uniform. For example, ultrathin seedlayers may have voids or other nonuniform physical properties that canresult in nonuniformities in the material deposited onto the seed layer.Such challenges may be overcome by enhancing the seed layers or forminga seed layer directly on a barrier layer to provide competent seedlayers that are well suited for depositing metals into trenches or holeswith small critical dimensions. One technique for enhancing the seedlayer or forming a seed layer directly on a barrier layer is toelectroplate a material using a processing solution with a lowconductivity. Such low conductivity processing fluids have relativelylow hydrogen ion (H⁺) concentrations, i.e., relatively high pH. Suitableelectrochemical processes for forming competent seed layers using lowconductivity processing fluids are disclosed in U.S. Pat. No. 6,197,181,which is herein incorporated by reference.

Electroplating onto seed layers or electroplating materials directlyonto barrier layers using low conductivity/high pH processing fluidspresents additional challenges. For example, inert anodes are generallyrequired when high pH processing fluids are used because the high pHtends to passivate consumable anodes. Such passivation may produce metalhydroxide particles and/or flakes that can create defects in themicrofeatures. Use of inert anodes is not without its drawbacks. Thepresent inventors have observed that when inert anodes are used, theresistivity of the deposited material increases significantly over arelatively small number of plating cycles. One way to combat thisincrease in the resistivity of the deposited material is to frequentlychange the processing fluid; however, this solution increases theoperating cost of the process.

As a result, there is a need for electrolytic processes for treatingmicrofeature workpieces that reduce adverse impacts created by thepresence of complexing agents and/or other additives and also maintaindeposit resistivity within desired ranges.

SUMMARY

The embodiments described herein relate to processes forelectrolytically processing a microfeature workpiece to deposit copperions or remove copper from surfaces of microfeature workpieces. Incertain embodiments, the processes are capable of producing depositsthat exhibit resistivity values within desired ranges over an extendednumber of plating cycles. The embodiments described herein also relateto processes that reduce the adverse impacts created by the presence ofcomplexing agents and/or other additives in processing fluids used toelectrolytically process a microfeature workpiece. In some embodiments,the described processes employ low conductivity/high pH processingfluids without suffering from the drawback of defect formation in thedeposited material resulting from the presence of metal hydroxideparticles or flakes present in processing fluids in contact with themicrofeature workpiece. Processors of microfeature workpieces will findcertain processes described herein desirable because the processesproduce high yields of deposits that exhibit resistivity values withinacceptable ranges without requiring costly frequent replacement ofprocessing fluids. Reducing adverse impacts created by the presence ofcomplexing agents and/or other additives in the processing fluids mayalso be considered desirable by users of the electrolytic processesdescribed herein.

In one embodiment, a surface of a microfeature workpiece is contactedwith a first processing fluid that includes first processing fluidspecies, such as a copper ion, an anion, and a complexing agent. Acounter electrode is in contact with a second processing fluid and anelectrochemical reaction occurs at the counter electrode. The processeffectively prevents movement of cationic species between the firstprocessing fluid and the second processing fluid. In certainembodiments, the first processing fluid can be a high pH processingfluid, the copper ion can be deposited onto the surface of themicrofeature workpiece, and the counter electrode can be an inertelectrode.

In another embodiment, a surface of a microfeature workpiece iscontacted with a first processing fluid that includes a copper ion to bedeposited onto the surface of the microfeature workpiece. In addition,the first processing fluid includes a complexing agent and a counteranion to the copper ion. An inert anode is in contact with a secondprocessing fluid, and an oxidizing agent is produced at the inert anode.The process employs an anion permeable barrier between the firstprocessing fluid and the second processing fluid. The anion permeablebarrier allows counter anions to pass from the first processing fluid tothe second processing fluid. In this embodiment, copper ions in thefirst processing fluid are deposited onto the surface of themicroelectronic workpiece. In certain embodiments, the first and secondprocessing fluids can be high pH processing fluids.

In a further embodiment, a surface of a microfeature workpiece iscontacted with a first processing fluid that includes a copper ion to bedeposited onto a surface of the microelectronic workpiece. In thisembodiment, an inert anode is in contact with a second processing fluidthat includes a buffer and pH adjustment agent and an anion permeablebarrier is located between the first processing fluid and the secondprocessing fluid.

The processes summarized above can be carried out in a system forelectrolytically processing a microfeature workpiece. The systemincludes a chamber that has a processing unit for receiving a firstprocessing fluid and counter electrode unit for receiving a secondprocessing fluid. A counter electrode is located in the counterelectrode unit, and an anion permeable barrier is located between theprocessing unit and the counter electrode unit. The chamber furtherincludes a source of copper ion in fluid communication with theprocessing unit and a source of a pH adjustment agent in fluidcommunication with the counter electrode unit.

Through the use of processes described above and the system describedabove, copper can be deposited onto surfaces of a microfeatureworkpiece. Such surfaces can take the form of seed layers or barrierlayers.

The process embodiments and system described above can be used toelectroplate materials onto a surface of a microfeature workpiece orused to electroetch or deplate materials from a surface of amicrofeature workpiece. When the process is used to electroplatematerials, the microfeature workpiece will function as a cathode, andthe counter electrode will function as an anode. In contrast, whendeplating is carried out, the microfeature workpiece will function as ananode, and the counter electrode will function as a cathode.

Accordingly, in another embodiment, a surface of a microfeatureworkpiece is contacted with a first processing fluid that includes acounter ion to copper on the surface. A cathode is contacted with asecond processing fluid also containing a counter ion, and an anionpermeable barrier is located between the first processing fluid and thesecond processing fluid. Chemical species in the second processing fluidare reduced, and an acid is introduced to the second processing fluid.Counter ions from the second processing fluid are passed through theanion permeable barrier to the first processing fluid. In accordancewith this embodiment, copper from the surface of the microfeatureworkpiece is electrolytically dissolved, i.e., oxidized and deplated.

The process summarized in the previous paragraph can be carried out in asystem for electrolytically processing a,microfeature workpiece thatincludes a chamber that has a processing unit for receiving a firstprocessing fluid and a counter electrode unit for receiving a secondprocessing fluid. An anion permeable barrier is positioned between theprocessing unit and the counter electrode unit. The system furtherincludes a cathode in the counter electrode unit, a source of coppercounter ions in fluid communication with the counter electrode unit, anda source of pH adjustment agent in fluid communication with theprocessing unit.

Through the use of the processes and systems described above forremoving copper from surfaces of a microfeature workpiece, copper can bedeplated from a microfeature workpiece surface.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing aspects and many of the attendant advantages of theprocesses described herein will become more readily appreciated as thesame become better understood by reference to the following detaileddescription, when taken in conjunction with the accompanying drawings,wherein:

FIG. 1 is a schematic illustration of a reactor for carrying outprocesses described herein;

FIG. 2 graphically illustrates deposit resistivity as a function of bathage for a deposit formed using processing fluids separated by an anionpermeable barrier and a deposit formed using a processing fluid withoutan anion permeable barrier;

FIG. 3 is a schematic illustration of a chamber for carrying outprocesses described herein;

FIG. 4 is a schematic illustration of the chemistry and chemicalreactions occurring in one embodiment of the processes forelectroplating a metal described herein;

FIG. 5 is a schematic illustration of the chemistry and chemicalreactions occurring in one embodiment of the processes forelectroplating two metals described. herein using an inert anode;

FIG. 6 is a schematic illustration of the chemistry and chemicalreactions occurring in one embodiment of the processes forelectroplating two metals described herein using a consumable anode;

FIG. 7 is a schematic illustration of the chemistry and chemicalreactions occurring in one embodiment of the processes for deplating ametal described herein;

FIG. 8 is a schematic illustration of a tool that includes chambers forcarrying out processes described herein;

FIGS. 9A-9C are schematic illustrations of one embodiment of theprocesses described herein for electrolytically treating a seed layer;and

FIGS. 10A and 10B are schematic illustrations of one embodiment of theprocesses described herein for electrolytically treating a barrierlayer.

DETAILED DESCRIPTION

As used herein, the terms “microfeature workpiece” or “workpiece” referto substrates on and/or in which micro devices are formed. Suchsubstrates include semiconductive substrates (e.g., silicon wafers andgallium arsenide wafers), nonconductive substrates (e.g., ceramic orglass substrates), and conductive substrates (e.g., doped wafers).Examples of micro devices include microelectronic circuits orcomponents, micromechanical devices, microelectromechanical devices,micro optics, thin film recording heads, data storage elements,microfluidic devices, and other small scale devices.

In the description that follows regarding electroplating a metal onto amicrofeature workpiece, specific reference is made to copper as anexample of a metal ion that can be electroplated onto a microfeatureworkpiece. The reference to copper ions is for exemplary purposes, andit should be understood that the following description is not limited tocopper ions. Examples of other metal ions useful in the processesdescribed herein include gold ions, tin ions, silver ions, platinumions, lead ions, cobalt ions, zinc ions, nickel ions, ruthenium ions,rhodium ions, iridium ions, osmium ions, rhenium ions, and palladiumions.

In the description that follows regarding electroplating more than onemetal onto a microfeature workpiece, specific reference is made to atin-silver solder system as an example of metal ions that can beelectroplated onto a microfeature workpiece to form a composite deposit.The reference to deposition of a tin-silver solder is for exemplarypurposes, and it should be understood that the description is notlimited to tin and silver ions.

With respect to the description that follows regarding deplating a metalfrom a microfeature workpiece, specific reference is made to copper asan example of a metal ion that can be deplated from a microfeatureworkpiece. The, reference to copper is for exemplary purposes, and itshould be understood that the description regarding deplating are notlimited to the removal of copper. Examples of other metals that can beremoved from a microfeature workpiece in accordance with embodimentsdescribed herein include gold ions, tin ions, silver ions, platinumions, lead ions, cobalt ions, zinc ions, nickel ions, ruthenium ions,rhodium ions, iridium ions, osmium ions, rhenium ions, and palladiumions.

Processes described herein can be carried out in an electrochemicalreactor, e.g., an electroplating or deplating reactor, such as the onedescribed below with reference to FIG. 1. Referring to FIG. 1, reactor10 includes an upper processing unit 12 containing a first processingfluid 14 (e.g., a catholyte in an electroplating process or an anolytein a deplating process) and a counter electrode unit 18 below theprocessing unit 12 that contains a -second processing fluid 20 (e.g.,anolyte in an electroplating process or a catholyte in a deplatingprocess) which may be different in composition and/or properties fromthe first processing fluid 14. Processing unit 12 receives a workingelectrode 16 (e.g., a microfeature workpiece) and delivers firstprocessing fluid 14 to the working electrode 16. Counter electrode unit18 includes a counter electrode 22 that is in contact with the secondprocessing fluid 20. When copper is to be deposited onto workingelectrode 16, working electrode 16 is the cathode and counter electrode22 is the anode. Accordingly, in plating applications, first processingfluid 14 is a catholyte, and second processing fluid 20 is an anolyte.In general, the catholyte contains components in the form of ionicspecies, such as acid ions, hydroxyl ions, and metal ions, and acomplexing agent capable of forming a complex with the metal ions. Thecatholyte may also include organic components, such as accelerators,suppressors, and levelers that improve the results of the electroplatingprocess. In addition, the catholyte may include a pH adjustment agent toaffect the pH of the catholyte. The anolyte generally includes ionicspecies as well, such as acid ions, hydroxyl ions, and metal ions. Thecatholyte may also include a pH adjustment agent. Additional detailsregarding the various components in the catholyte and anolyte areprovided below.

When copper is to be deplated from working electrode 16, workingelectrode 16 is the anode, and counter electrode 22 is the cathode.Accordingly, in deplating applications, the first processing fluid 14 isan anolyte, and the second processing fluid 20 is a catholyte.

Reactor 10 also includes a nonporous anion permeable barrier 24 betweenthe first processing fluid 14 and the second processing fluid 20.Nonporous anion permeable barrier 24 allows anions to pass through thebarrier while inhibiting or substantially preventing non-anioniccomponents, such as cations, from passing between the first processingfluid 14 and second processing fluid 20. By inhibiting or substantiallypreventing nonionic components from passing between the first processingfluid 14 and second processing fluid 20, adverse effects on thedeposited material resulting from the presence of unwanted nonanioniccomponents, such as cations, in the first processing fluid 14 can beavoided. As such, nonporous anion permeable barrier 24 separates firstprocessing fluid 14 and second processing fluid 20 such that firstprocessing fluid 14 can have different chemical characteristics andproperties than second processing fluid 20. For example, the chemicalcomponents of first processing fluid 14 and second processing fluid 20can be different, the pH of first processing fluid 14 and secondprocessing fluid 20 can be different, and concentrations of componentscommon to both first processing fluid 14 and second processing fluid 20can be different.

In the following description of an electroplating process, forconsistency, working electrode 16 will be referred to as the cathode,and counter electrode 22 will be referred to as the anode. Likewise,first processing fluid 14 will be referred to as the catholyte, andsecond processing fluid 20 will be referred to as the anolyte. Whenreactor 10 is used to electrolytically process a microfeature workpieceto deposit metal ions thereon, an electric potential is applied betweenanode 22 and cathode 16. Copper ions in the catholyte are consumed bythe deposition of copper ions onto the cathode. Meanwhile, the anodebecomes positively charged and attracts negatively charged ions to itssurface. For example, hydroxyl ions in the anolyte are attracted to theanode where they react to liberate oxygen and produce water. Theforegoing results in a gradient of charge in the anolyte with unbalancedpositively charged species in the anolyte solution, and negativelycharged species in the catholyte solution. This charge imbalanceencourages the transfer of negatively charged anions through the anionpermeable barrier 24 from catholyte 14 to the anolyte 20. Anelectrochemical reaction (e.g., losing or gaining electrons) occurs atcathode 16, resulting in metal ions being reduced (i.e., gainingelectrons) to metal on surfaces of cathode 16.

Reactor 10 effectively maintains the concentration of metal ions incatholyte 14 during the electroplating process in the following manner.As metal ions are deposited onto the surface of cathode 16, additionalmetal ions are introduced to catholyte 14 from a source of metal ions130, which is in fluid communication with processing unit 12. Asexplained below in more detail, these metal ions can be provided bydelivering a metal salt solution to processing unit 12. Processing unit12 can also be in fluid communication with sources of other componentsthat need replenishment. In a similar fashion, counter electrode unit 18may be in fluid communication with sources of components that requirereplenishment. For example, counter electrode unit 18 can be in fluidcommunication with a source of pH adjustment agent 132. Likewise, bothprocessing unit 12 and electrode unit 18 can include conduits or otherstructures for removing portions of catholyte 14 from processing unit 12or portions of anolyte 20 from counter electrode unit 18.

Anode 22 may be a consumable anode or an inert anode. Exemplaryconsumable anodes and inert anodes are described below in more detail.

Referring to FIG. 4, the chemistry present in processing unit 12 andcounter electrode unit 18 are described in more detail along withvarious chemical reactions that are believed to occur. It should beunderstood that by describing chemical reactions that are believed tooccur within reactor 10, the processes described herein are not limitedto processes wherein these reactions occur.

FIG. 4 schematically illustrates an example of the operation of reactor10 using an anion permeable barrier 24 and an inert anode 22 incombination with a low conductivity/high pH first processing fluid and alow conductivity/high pH second processing fluid suitable for processingcopper seed layers or plating directly onto a barrier layer. In thedescription that follows, high pH first processing fluid 14 inprocessing unit 12 is a catholyte containing a metal ion (M⁺), e.g.,copper ions (Cu²⁺), a counter ion (X⁻) for the metal ion, e.g., sulfateions (SO₄ ²⁻), a complexing agent CA, as described below, chelated withthe metal ions, a pH buffer such as boric acid (H₃BO₃) that dissociatesinto hydrogen ions (H⁺) and H₂BO₃−, and a pH adjustment agent, such astetramethylammonium hydroxide (TMAH) that dissociates into hydroxyl ion(OH⁻) and TMA⁺. The specific hydrogen ion concentration in catholyte 14can be chosen taking into consideration conventional factors such ascomplexing ability of the complexing agent, buffering capability of thebuffer, metal ion concentrations, volatile organics concentrations,deposition potential of the complex at the particular pH, solubility ofthe catholyte constituents, stability of the catholyte, desiredcharacteristics of the deposits, and diffusion coefficients of the metalions.

For example, for electroplating embodiments, high pH second processingfluid 20 in counter electrode unit 18 is an anolyte. Anolyte 20 can havea concentration of H⁺ that is approximately equal to the concentrationof H⁺ in catholyte 14, although this is not required. By adjusting H⁺concentration in anolyte 20 to be approximately equal to theconcentration of H⁺ in catholyte 14, transfer of negatively chargedhydroxyl ions from catholyte 14 to anolyte 20 through anion permeablemembrane 24 during electroplating is inhibited. By inhibiting thetransfer of negatively charged hydroxyl ions from catholyte 14 toanolyte 20, a more constant catholyte pH can be maintained. Bymaintaining pH of the catholyte relatively constant, the need to add pHadjustment agent to the catholyte is reduced or eliminated. Thissimplifies maintenance of the catholyte and helps to maintain theconductivity of the catholyte relatively stable through repeated platingcycles. In the description that follows with reference to FIG. 4,anolyte 20 includes a pH adjustment agent, such as TMAH, and a buffer,such as boric acid.

As mentioned above, during a plating cycle, an electric potential isapplied between cathode 16 and anode 22. As copper ions are reduced andelectroplated onto cathode 16, sulfate ions (SO₄ ²⁻) accumulate in thecatholyte near a first surface 32 of anion permeable barrier 24.Additionally, depending on the pH of the anolyte at positively chargedanode 22, hydroxyl ions (OH⁻) are converted to water (H₂O) and oxygen(O₂) and/or water is decomposed to hydrogen ions (H⁺) and oxygen. Theresulting electrical charge gradient causes the negatively chargedsulfate ions to move from first surface 32 of anion permeable barrier 24to the second surface 34 of anion permeable barrier 24. The transfer ofnegatively charged sulfate ions from catholyte 14 to anolyte 20 duringthe plating cycle maintains the charge balance of reactor 10. Tomaintain the concentration of the negatively charged ions resulting fromthe dissociation of boric acid in catholyte 14 during electroplating,the concentration of boric acid in the anolyte may be set so it issignificantly greater than the concentration of boric acid in thecatholyte. This concentration differential inhibits the negativelycharged ions resulting from the dissociation of boric acid in catholyte14 from moving through anion permeable membrane 24 to anolyte 20 duringelectroplating.

Continuing to refer to FIG. 4, during a plating cycle, as explainedabove, copper ions in catholyte 14 are reduced at cathode 16 and aredeposited as copper. Copper ions that are consumed by the electroplatingare replenished by the addition of a solution of copper sulfate to thecatholyte. During the plating cycle, sulfate ions which are introducedto catholyte 14 as a result of adding the copper sulfate transfer acrossanion permeable barrier 24 to anolyte 20. Portions of the anolyte can beremoved from counter electrode unit (18 in FIG. 1) in order to avoid theexcessive build up of sulfate ions in the anolyte 20. Non-anioniccomponents in catholyte 14 (e.g., Cu²⁺, H⁺, TMA⁺, H₃BO₃, and Cu(ED)₂ ²⁺)generally do not pass through anion permeable membrane 24 and thusremain in catholyte 14. As described above, transfer of the hydroxyl(OH⁻) ion from the catholyte to the anolyte is minimized by maintainingpH of anolyte 20 at substantially the same level as pH of catholyte 14.Since hydroxyl ions are consumed at anode 22, a pH adjustment agent,such as TMAOH, may be added to anolyte 20 as described above to maintainthe pH of the anolyte at desired levels.

Microfeature workpieces that can be processed using processes describedherein can include different structures on their surfaces that can beelectrolytically processed to deposit materials thereon. For example, asemiconductor microfeature workpiece can include seed layers or barrierlayers. Referring to FIGS. 9A-9C, one sequence of steps forelectrolytically processing a seed layer using a process describedherein is provided.

Referring to FIG. 9A, a cross-sectional view of a microstructure, suchas trench 105 that is to be filled with bulk metallization isillustrated and will be used to describe use of processes describedherein to enhance a seed layer. As shown, a thin barrier layer 110, forexample, titanium nitride or tantalum nitride, is deposited over thesurface of a semiconductor device or, as illustrated in FIG. 9A, over alayer of dielectric 108 such as silicon dioxide. Any known techniquesuch as chemical vapor deposition (CVD) or physical vapor deposition(PVD), can be used to deposit barrier layer 110.

After deposition of barrier layer 110, an ultrathin copper seed layer115 is deposited on barrier layer 110. The resulting structure isillustrated in FIG. 9B. Seed layer 115 can be formed using a vapordeposition technique also, such as CVD or PVD. Alternatively, seed layer115 can be formed by direct electroplating onto barrier layer 110 asdescribed below in more detail. Owing to the small dimensions of trench105, techniques used to form ultrathin seed layer 115 should be capableof forming the seed layer without closing off small geometry trenches.In order to avoid closing off small geometry trenches, seed layer 115should be as thin as possible while still providing a suitable substrateupon which to deposit bulk metal. For example, ultrathin seed layer 115can have a thickness of about 50 to about 500 angstroms, about 100 toabout 250 angstroms, or specifically about 200 angstroms.

The use of ultrathin seed layer 115 introduces its own set of drawbacks.For example, ultrathin seed layers may not coat the barrier layer in auniform manner. For example, voids or non-continuous seed layer regionson the sidewalls of the trenches such as at 120, can be present inultrathin seed layer 115. The processes described herein can be used toenhance seed layer 115 to fill the void or non-continuous regions 120found in ultrathin seed layer 115. Referring to FIG. 9C, to achieve thisenhancement, the microfeature workpiece is processed as described hereinto deposit a further amount of metal 118 onto ultrathin seed layer 115and/or portions of underlying barrier layer 110 that are exposed atvoids or non-continuous portions 120.

Preferably, this seed layer enhancement continues until a sidewall stepcoverage, i.e., the ratio of seed layer 115 thickness at the bottomsidewall regions to the nominal thickness of seed layer 115 at theexteriorly disposed side of the workpiece, achieves a value of at least10%. More preferably, the sidewall step coverage is at least about 20%.Preferably, such sidewall step coverage values are present insubstantially all of the recessed structures of the microfeatureworkpiece; however, it will be recognized that certain recessedstructures may not-reach such sidewall step values.

Another type of feature on the surface of a microfeature workpiece thatcan be electrolytically treated using processes described herein is abarrier layer. Barrier layers are used because of the tendency ofcertain metals to diffuse into silicon junctions and alter theelectrical characteristics of semiconductor devices formed in asubstrate. Barrier layers made of materials such as titanium, titaniumnitride, tantalum, tantalum nitride, tungsten, and tungsten nitride areoften laid over silicon junctions and any intervening layers prior todepositing a layer of metal. Referring to FIG. 10A, a cross-sectionalview of a microstructure, such as trench 205 that is to be filled withbulk metallization is illustrated, and will be used to describe theformation of a metal layer directly onto a barrier layer using processesdescribed herein. As illustrated in FIG. 10A, thin barrier layer 210 isdeposited over the surface of a semiconductor device or, as illustratedin FIG. 10A, over a layer of dielectric 208, such as silicon dioxide.Barrier layer 210 can be deposited as described above with reference toFIG. 9A using CVD or PVD techniques. After barrier layer 210 isdeposited, the microfeature workpiece is processed as described hereinto form a metal feature 215 over barrier layer 210. The resultingstructure can then be further processed to deposit bulk metal (notshown) to fill the trench 205.

The pH of processing fluids described herein can vary from alkaline toacidic. The low conductivity/high pH processing fluids described hereinare distinct from low pH processing fluids such as acidic electroplatingbaths. The concentration of H⁺ useful in high pH processing fluids mayvary with those providing pHs above 7, preferably above 8 and mostpreferably above 9 being examples of useful high pH processing fluids.

As noted above, processes described herein are useful to electroplatemetals other than copper, for example, gold, silver, platinum, nickel,tin, lead, ruthenium, rhodium, iridium, osmium, rhenium, and palladium.Metal ions useful in the catholyte can be provided from a solution of ametal salt. Exemplary metal salts include gluconates, cyanides,sulfamates, citrates, fluoroborates, pyrophosphates, sulfates,chlorides, sulfides, chlorites, sulfites, nitrates, nitrites, andmethane sulfonates. Exemplary concentrations of metal salts in thecatholyte used for plating applications range from about 0.03 to about0.25M.

The ability to electroplate metal ions can be affected by chelating themetal ion with a complexing agent. In the context of the electroplatingof copper, copper ions chelated with ethylene diamine complexing agentexhibit a higher deposition potential compared to copper ions that havenot been chelated. Complexing agents useful for chelating and formingcomplexes with metal ions include chemical compounds having at least onepart with the chemical structure COOR₁—COHR₂R₃ where R₁ is an organicgroup covalently bound to the carboxylate group (COO), R₂ is eitherhydrogen or an organic group, and R₃ is either hydrogen or an organicgroup. Specific examples of such type of complexing agents includecitric acid and salts thereof, tartaric acid and salts thereof,diethyltartrate, diisoproyltartrate, and dimethyltartrate. Another typeof useful complexing agent includes compounds that contain a nitrogencontaining chelating group R—NR₂—R₁, wherein R is any alkyl or aromaticgroup, and R₁ and R₂ are H, alkyl, or aryl organic groups or polymerchains. Specific examples of these types of complexing agents includeethylene diamine, ethylene diamine tetraacetic acid and its salts,cyclam, porphrin, bipyridyl, pyrolle, thiophene, and polyamines. Inplating embodiments, suitable ratios between the concentration of metalions and concentrations of complexing agents in the catholyte can rangefrom 1:25 to 25:1; for example, 1:10 to 10:1 or 1:5 to 5:1.

Useful pH adjustment agents include materials capable of adjusting thepH of the first processing fluid and the second processing fluid, forexample, to above 7 to about 13, and more specifically, above about 9.0.When ethylene diamine or citric acid are used as a complexing agent forcopper ions, a pH of about 9.5 is useful. When ethylene diaminetetraacetic acid is used as a complexing agent for copper ions, a pH ofabout 12.5 is suitable. Examples of suitable pH adjustment agentsinclude alkaline agents such as potassium hydroxide, ammonium hydroxide,tetramethyl ammonium hydroxide, sodium hydroxide, and other alkalinemetal hydroxides. A useful amount and concentration of pH adjustmentagents will depend upon the level of pH adjustment desired and otherfactors, such as the volume of processing fluid and the other componentsin the processing fluid. Useful pH adjustment agents also includematerials capable of adjusting the pH of the first and second processingfluid to below 7.

Useful buffers include materials that maintain the pH relativelyconstant, preferably at a level that facilitates complex formation anddesirable complexed species. Boric acid was described above as anexample of a suitable buffer. Other useful buffers include sodiumacetate/acetic acid and phosphates. Exemplary concentrations of bufferrange from about 0.01 to about 0.5M in the catholyte for platingapplications.

The catholyte can include other additives such as those that lower theresistivity of the fluid, e.g., ammonium sulfate; and those thatincrease the conformality of the deposit, e.g., ethylene glycol. Forplating applications, exemplary concentrations of resistivity effectingagents in the catholyte range from about 0.01 to about 0.5M. Forconformality affecting agents concentrations ranging from about 0 to1.0M are exemplary.

Useful anion permeable barriers include nonporous barriers, such assemi-permeable anion exchange membranes. A semi-permeable anion exchangemembrane allows anions to pass but not non-anionic species, such ascations. The nonporous feature of the barrier inhibits fluid flowbetween first processing fluid 14 and second processing fluid 20 withinreactor 10 in FIG. 1. Accordingly, an electric potential, a chargeimbalance between the processing fluids, and/or differences in theconcentrations of substances in the processing fluids can drive anionsacross an anion permeable barrier. In comparison to porous barriers,nonporous barriers are characterized by having little or no porosity oropen space. In a normal electroplating reactor, nonporous barriersgenerally do not permit fluid flow when the pressure differential acrossthe barrier is less than about 6 psi. Because the nonporous barriers aresubstantially free of open area, fluid is inhibited from passing throughthe nonporous barrier. Water, however, may be transported through thenonporous barrier via osmosis and/or electro-osmosis. Osmosis can occurwhen the molar concentration in the first and second processing fluidsare substantially different. Electro-osmosis occurs as water is carriedthrough the nonporous barrier with current-carrying ions in the form ofa hydration sphere. When the first and second processing fluids havesimilar molar concentrations and no electrical current is passed throughthe processing fluids, fluid flow between the first and secondprocessing fluids via the nonporous barrier is substantially prevented.

A nonporous barrier can be hydrophilic so that bubbles in the processingfluids do not cause portions of the barrier to dry, which reducesconductivity through the barrier. Exemplary nonporous barriers includeIonac® membranes manufactured by Sybron Chemicals, Inc., and NeoSepta®manufactured by Asahi Kasei Company.

In addition to the nonporous barriers described above, anion permeablebarrier can also be a porous barrier. Porous barriers includesubstantial amounts of open area or pores that permit fluid to passthrough the porous barrier. Both ionic materials and nonionic materialsare capable of passing through a porous barrier; however, passage ofcertain materials may be limited or restricted if the materials are of asize that allows the porous barrier to inhibit their passage. Whileuseful porous barriers may limit the chemical transport (via diffusionand/or convection) of some materials in the first processing fluid andthe second processing fluid, they allow migration of anionic species(enhanced passage of current) during application of electric fieldsassociated with electrolytic processing. In the context of electrolyticprocessing a useful porous barrier enables migration of anionic speciesacross the porous barrier while substantially limiting diffusion ormixing (i.e., transport across the barrier) of larger organic componentsand other non-anionic components between the anolyte and catholyte.Thus, porous barriers permit maintaining different chemical compositionsfor the anolyte and the catholyte. The porous barriers should bechemically compatible with the processing fluids over extendedoperational time periods. Examples of suitable porous barrier layersinclude porous glasses (e.g., glass frits made by sintering fine glasspowder), porous ceramics (e.g., alumina and zirconia), silica aerogel,organic aerogels (e.g., resorcinol formaldehyde aerogel), and porouspolymeric materials, such as expanded Teflon® (Gortex®). Suitable porousceramics include grade P-6-C available from CoorsTek of Golden, Colo. Anexample of a porous barrier is a suitable porous plastic, such asKynar™, a sintered polyethylene or polypropylene. Suitable materials canhave a porosity (void faction) of about 25%-85% by volume with averagepore sizes ranging from about 0.5 to about 20 micrometers. Such porousplastic materials are available from Poretex Corporation of Fairburn,Ga. These porous plastics may be made from three separate layers ofmaterial that include a thin, small pore size material sandwichedbetween two thicker, larger pore-sized sheets. An example of a productuseful for the middle layer having a small pore size is CelGard™ 2400,made by CelGard Corporation, a division of Hoechst, of Charlotte, N.C.The outer layers of the sandwich construction can be a material such asultra-fine grade sintered polyethylene sheet, available from PoretexCorporation. Porous barrier materials allow fluid flow across themselvesin response to the application of pressures normally encountered in anelectrochemical treatment process, e.g., pressures normally ranging fromabout 6 psi and below.

Inert anodes useful in processes described herein are also referred toas non-consumable anodes and/or dimensionally stable anodes and are ofthe type that when an electric potential is applied between a cathodeand an anode in contact with an electrolyte solution, that there is nodissolution of the chemical species of the inert anode. Exemplarymaterials for inert anodes include platinum, ruthenium, ruthenium oxide,iridium, and other noble metals.

Consumable anodes useful in processes described herein are of the typethat when an electric potential is applied between a cathode and ananode in contact with an electrolyte solution, dissolution of thechemical species making up the anode occurs. Exemplary materials forconsumable anodes will include those materials that are to be depositedonto the microfeature workpiece, for example, copper, gold, tin, silver,lead, platinum, nickel, cobalt, zinc, and the like. The temperature ofthe processing fluids can be chosen taking into considerationconventional factors such as complexing ability of the complexing agent,buffering capability of the buffer, metal ion concentration, volatileorganics concentration, deposition potential of the complexed metal atthe particular pH, solubility of the processing fluid constituents,stability of the processing fluids, desired deposit characteristics, anddiffusion coefficients of the metal ions. Generally, temperaturesranging from about 20° C.-35° C. are suitable, although temperaturesabove or below this range may be useful.

As described above in the context of an electroplating process,oxidation of hydroxyl ions or water at the anode produces oxygen capableof oxidizing components in the catholyte. When an anion permeablebarrier is absent, oxidation of components in the electrolyte can alsooccur directly at the anode. Oxidation of components in the electrolyteis undesirable because it is believed that the oxidized componentscontribute to variability in the properties (e.g. resistivity) of themetal deposits. Through the use of an anion permeable barrier, asdescribed above, transfer of oxygen generated at the anode from theanolyte to the catholyte is minimized and/or prevented, and, thus, suchoxygen is not available to oxidize components that are present in thecatholyte. As discussed above, one way to address the problem of oxygengenerated at the anode oxidizing components in the processing fluid isto frequently replace the processing fluid. Because of the time and costassociated with frequently replacing the processing fluid, the processesdescribed herein provide an attractive alternative by allowing theprocessing fluids to be used in a large number of plating cycles withoutreplacement. Use of the anion permeable barrier also isolates the anodefrom non-anionic components in the catholyte, e.g., complexing agent,that may otherwise be oxidized at the anode and adversely affect theability of the catholyte to deposit features having resistivityproperties that fall within acceptable ranges.

The resistivity of deposited metals as a function of the age of theprocessing fluid from which the deposit was formed is illustrated inFIG. 2. FIG. 2 illustrates how the use of processes described herein todeposit copper significantly extends the useful operating life of acatholyte compared to conventional processes using similar chemistrieswithout an anion permeable barrier. FIG. 2 illustrates test resultsevaluating the resistivity of several 20 nanometer copper seed layersdeposited using the same chemistry in contact with the workpiece. Oneset of copper seed layers was formed using a process that did not employan anion permeable barrier and a second set of copper seed layers wasformed using a process that employed an anion permeable barrier inaccordance with a process described herein. More specifically theresistivity of a deposit was measured using a 4-pt resistivity probefrom Creative Design Engineering, Inc. that measures the sheetresistance of a substrate. The resistivity of the copper films wasobtained as the product of sheet resistance and thickness of the thinfilm. Several wafers with the same seed layer resistance were obtained,and their sheet resistance was pre-measured (R_(PVD)). The wafers werethen plated in a chamber with no membranes, inert anodes, and a 9.5 pHelectrolyte. A fixed amp time was applied for each wafer (0.7 amp-minfor a 300 mm wafer corresponding to 20 nm Cu thickness), and atheoretical amount of Cu film deposited on the seed layer was obtainedat the same current density. The wafers were then rinsed and dried in aspin rinse dryer. The wafers were then measured in the 4-pt probe again.This provided a post sheet resistance measurement (R_(total)). With thetwo sheet resistance measurements, the sheet resistance of just the filmdeposited was obtained through the method of parallel subtraction usingthe formula shown below and the sheet of resistance of theelectrodeposited seed layer was obtained.R _(ECD Seed)=(R _(PVD) *R _(total))/(R _(PVD) −R _(total))

The resistivity of the deposited film was obtained by multiplying thethickness by the sheet resistance calculated above.

Resistivity of the electrodeposit=Thickness*R_(ECD Seed)=20nm*R_(ECD Sed)

Several such wafers were plated periodically, as the bath ages in termsof amp-min (dummy wafers were plated to age the bath).

Similar sets of wafers were plated using an anionic membrane asdescribed herein. The chamber utilized the same electrolyte as thecatholyte used to plate the first set of wafers described above. Theanolyte was a fluid consisting of buffer, pH adjustment agent, and ofthe same pH as the catholyte as described herein. The wafers were platedwith the same amp time as before under substantially identicalconditions.

Similar calculations were performed and the resistivity of theelectrodeposit was obtained as a function of bath age.

The resistivity of seed layers deposited using a process without ananion permeable barrier (line 38), increases rapidly with the age of thebath, increasing more than three times in under 2000 amp minutes. Bycomparison, the resistivity of copper seed layers deposited using aprocess that employed an anion permeable membrane as described herein,illustrated by line 40, increases only gradually over time such thatlittle increase is observed even after 10,000 amp minutes. These resultsillustrate how a process described herein substantially extends theuseful life of processing fluids used to deposit metal features onto amicrofeature workpiece.

Another advantage of employing an anionic permeable barrier in theprocesses described herein is that the barrier prevents bubbles from theoxygen gas evolved at the anode from transferring to the catholyte.Bubbles in the catholyte are undesirable because they can cause voids orholes in the deposited features.

Another feature of processes described herein is that the pH adjustmentagent, e.g., tetramethyl ammonium hydroxide, does not accumulate in thefirst processing fluid. As a result, pH adjustment agent need not beremoved from the first processing fluid. This simplifies the maintenanceof the first processing fluid.

In the foregoing descriptions, copper has been used as an example of ametal that can be used to enhance a seed layer or to form a metalfeature directly onto a barrier layer. However, it should be understoodthat the basic principles of the processes described herein and theiruse for enhancement of an ultrathin metal layer prior to the bulkdeposition of additional metal or the direct electroplating of a metalonto a barrier layer can be applied to other metals or alloys as well asdeposition for other purposes. For example, gold is commonly used on forthin film head and III-V semiconductor applications. Gold ions can beelectroplated using chloride-or sulfite as the counter ion. As withcopper, the chloride or sulfite counter ion would migrate across theanionic permeable barrier as described above in the context of copper.Potassium hydroxide could be used as the pH adjustment agent in a goldelectroplating embodiment to counteract a drop in pH in the anolyteresulting from the oxidation of hydroxyl ions at the anode. As with thecopper example described above, in the gold embodiment, gold chloride orgold sulfite, in the form of sodium gold sulfite or potassium goldsulfite could be added to the catholyte to replenish the gold deposited.

As mentioned previously, processes described above are useful fordepositing more than one metal ion onto a microfeature workpiecesurface. For example, processes described above are useful fordepositing multi-component solders such as tin-silver solders. Othertypes of multi-component metal systems that can be deposited usingprocesses described above include tin-copper, tin-silver-copper,lead-tin, nickel-iron, and tin-copper-antimony. Unlike certain copperfeatures that are formed on the surfaces of microfeature workpieces,solder features tend to be used in packaging applications and are thuslarge compared to copper microfeatures. Because of their larger size,e.g., 10-200 microns, solder features are more susceptible to thepresence of bubbles in processing fluids that can become entrapped andaffect the quality of the solder deposits. A tin-silver solder system isan example of plating of a metal with multiple valence states.Generally, metals with multiple valence states can be plated from mostof their stable states. Since the charge required to deposit any metalis directly proportional to the electrons required for the reduction,metals in their valence states closest to their neutral states consumeless energy for reduction to metal. Unfortunately, most metals in theirstate closest to their neutral states are inherently unstable, andtherefore production-worthy plating can be unfeasible. Through the useof processes for plating metal ions described above, plating solutionsthat include metals in this inherently unstable state can be applied inan effective process to deposit the desired metal. Through the use ofthe processes described above for depositing a metal, less oxidation ofthe inherently unstable metal species occurs, thus providing a moreproduction-worthy process.

By way of illustration, most fin-silver plating solutions prefer Sn(II)as the species for tin plating. For such multi-component platingsystems, control of tin and silver ions needs to be precise, and the useof silver or tin as an anode is not feasible. The use of such consumableanodes could cause stability issues resulting from plating/reacting withthe anodes, and they also create issues relating to the ability touniformly replenish metal. On the other hand, the use of inert anodesavoids the foregoing issues, but introduces a new issue associated withthe production of oxygen through the oxidation of water or hydroxyl ionsat the inert anode. Such oxygen not only may oxidize other components inthe plating bath, it may also oxidize the desired Sn(II) species to themore stable Sn(IV) ion, which is more difficult to plate onto aworkpiece.

Referring to FIG. 5, a schematic illustration is provided for theoperation of reactor 10 using an anion permeable barrier 24 and an inertanode 22 in combination with a first processing fluid and a secondprocessing fluid suitable for depositing tin-silver solder. In thedescription that follows, processing fluid 14 in processing unit 12 is acatholyte containing metal ions M₁ ⁺ and M₂ ⁺, e.g., Sn²⁺ and Ag⁺ ions;counter ions X₁− and X₂− for the metal ions, e.g., methane sulfonateCH₃SO₃−; complexing agents CA₁ and CA₂, e.g., proprietary organicadditives, chelated with the metal ions. As discussed above in thecontext of the electroplating of copper, the specific hydrogen ionconcentration in catholyte 14 can be chosen taking into considerationconventional factors such as complexing ability of the complexing agent,buffering capability of the buffer, metal ion concentrations, volatileorganics concentrations, alloy deposition potential of the complex atthe particular pH, solubility of the catholyte constituents, stabilityof the catholyte, desired characteristics of the deposits, and diffusioncoefficients of the metal ions.

The discussions above regarding the concentration of H⁺ in the anolyteand catholyte, relative concentrations of the buffer in the anolyte andthe catholyte, use of the pH adjustment agent, replenishment of themetal ions, cathodic reduction reactions, and anodic oxidation reactionsin the context of the electroplating of copper are equally applicable toa tin-silver system. The particular operating conditions that are mostdesirable are related to the specific chemistry being used.

As with the copper plating process, an electric potential appliedbetween cathode 16 and anode 22 results in tin ions and silver ionsbeing reduced at cathode 16 and deposited thereon. The methane sulfonate(MSA) counter ion (CH₃SO₃−) accumulates in the catholyte near a firstsurface 32 of anion permeable barrier 24. As with the copper system, atpositively charged anode 22, hydroxyl ions are converted to water andoxygen and/or water is decomposed to hydrogen ions and oxygen. Theresulting electrical charge gradient causes negatively charged MSA ions(CH₃SO₃−) to move from first surface 32 of anion permeable barrier 24 tothe second surface 34 of anion permeable barrier 24. The transfer ofnegatively charged MSA ions (CH₃SO₃−) from catholyte 14 to anolyte 20during the plating cycle maintains the charge balance of reactor 10. Tinand silver ions that are deposited onto cathode 16 can be replenished bythe addition of a solution of tin methane sulfonate and silver methanesulfonate to the catholyte. During the plating cycle, MSA ions that areintroduced to catholyte 14 as a result of the addition of the tin MSAand silver MSA transfer across anion permeable barrier 24 to anolyte 20.As with the copper process, portions of the anolyte can be removed fromcounter electrode unit 18 to avoid the buildup of MSA ions in theanolyte.

Referring to FIG. 6, in a different embodiment, electroplating of twometals, e.g., tin and silver, can also be achieved using a consumableanode 122. Referring to FIG. 6, the catholyte 14 in processing unit 12is similar to the catholyte described with reference to FIG. 5. In theprocess depicted in FIG. 6, metal ion M₂ ⁺ is introduced into processingunit 12 from source 200, metal ion M₁ ⁺ is supplied to counter electrodeunit 18 through oxidation of metal making up consumable anode 122. Metalion M₁ ⁺ combines with counter ion X₁− to form the metal salt M₁X₁ incounter electrode unit 18 and is then delivered via line 202 toprocessing unit 12. Metal salt M₁X₁ delivered to processing unit 12dissociates therein to provide a source of metal ion M₁ ⁺ that can bereduced at cathode 16 and deposited thereon as described above withreference to FIG. 5. In accordance with this embodiment, complexingagents CA₁ and CA₂ are present in catholyte 14 where they can complexwith metal ions M₁ ⁺ and M₂ ⁺. Suitable pH adjustment agents and pHbuffers may be present and/or added to the catholyte and anolyte. Thecharge balance within reactor 10 can be maintained through the transferof negatively charged counter ion X₁− in processing unit 12 across anionpermeable membrane 24 into counter electrode unit 18.

Metal can be deplated from a microfeature workpiece by reversing thebias of the electric field created between the microfeature workpieceand the working electrode. Referring to FIG. 7, a microfeature workpiece416 is provided that carries a metal M, e.g., copper, on its surface.Microfeature workpiece 416 is contacted with a first processing fluid414 in processing unit 412. Processing fluid 414 includes metal ionsM²⁺, e.g., copper ions; a complexing agent CA, e.g., ethylene diaminetetraacetic acid; a metal salt MX, e.g., copper sulfate; a complexedmetal ion M(CA)²⁺; hydroxyl ions; a buffer, and a counter ion X²⁻, e.g.,sulfate ion. First processing unit 412 is separated from a counterelectrode unit 418 by anion permeable membrane 424. Counter electrodeunit 418 includes counter electrode 422 and a second processing fluid420. In a deplating process, microfeature workpiece 416, the workingelectrode, is an anode, and counter electrode 422 is the cathode.Processing unit 412 is also in fluid communication with a source 430 ofcomplexing agent CA and hydroxyl ions. In addition, processing unit 412can be provided with a mechanism 440 for removing metal salts therefrom.Counter electrode unit 418 is in fluid communication with a source 450of acid. Through the application of an electric potential between anode416 and cathode 422, hydrogen ions are reduced at the cathode 422 toproduce hydrogen gas. Copper on the surface of microfeature workpiece416 is oxidized resulting in copper ions being removed from the surfaceof the microfeature workpiece. The charge balance within reactor 410 ismaintained through the transfer of counter ion X²⁻ from catholyte 420 toanolyte 414 through anion permeable membrane 424.

Catholyte 420 in counter electrode unit 418 includes hydroxyl ions,buffer, and counter ion X²−. The acid that is added to counter electrodeunit 418 can be both a source of counter ion X²⁻ as well as a pHadjustment agent. In order to reduce or eliminate transfer of buffercomponents across anionic permeable membrane 424, the bufferconcentration in anolyte 414 can be maintained at a level equal to orgreater than the concentration of buffer in catholyte 420.

One or more of the reactors for electrolytically treating a microfeatureworkpiece or systems including such reactors may be integrated into aprocessing tool that is capable of executing a plurality of methods on aworkpiece. One such processing tool is an electroplating apparatusavailable from Semitool, Inc., of Kalispell, Mont. Referring to FIG. 5,such a processing tool may include a plurality of processing stations510, one or more of which may be designed to carry out an electrolyticprocessing of a microfeature workpiece with a high pH first processingfluid and an inert anode as described above. Other suitable processingstations include one or more rinsing/drying stations and other stationsfor carrying out wet chemical processing. The tool also includes arobotic member 520 that is carried on a central track 525 for deliveringworkpieces from an input/output location to the various processingstations.

Referring to FIG. 3, a more detailed schematic illustration of onedesign of a reactor 100 for electroplating metals onto seed layers,directly electroplating metal onto barrier layers, or otherwisedepositing materials onto workpieces is illustrated. Reactor 100includes a vessel 302, a processing chamber 310 configured to direct aflow of first processing fluid to a processing zone 312, and an anodechamber 320 configured to contain a second processing fluid separatefrom the first processing fluid. An anion permeable barrier 330separates the first processing fluid in the processing unit 310 from thesecond processing fluid in the anode chamber 320. Reactor 100 furtherincludes a workpiece holder 340 having a plurality of electricalcontacts 342 for applying an electric potential to a workpiece 344mounted to workpiece holder 340. Workpiece holder 340 can be a movablehead configured to position workpiece 344 in processing zone 312 ofprocessing unit 310, and workpiece holder 340 can be configured torotate workpiece 344 in processing zone 312. Suitable workpiece holdersare described in U.S. Pat. Nos. 6,080,291; 6,527,925; 6,773,560, andU.S. patent application Ser. No. 10/497,460; all of which areincorporated herein by reference.

Reactor 100 further includes a support member 350 in the processingchamber 310 and a counter electrode 360 in the anode chamber 320.Support member 350 spaces the anion permeable barrier 330 apart fromworkpiece processing zone 312 by a controlled distance. This featureprovides better control of the electric field at processing zone 312because the distance between the anion permeable barrier 330 andworkpiece processing zone 312 affects the field strength at processingzone 312. Support member 350 generally contacts first surface 332 ofanion permeable barrier 330 such that the distance between first surface332 and processing zone 312 is substantially the same across processingchamber 310. Another feature of support member 350 is that it alsoshapes anion permeable barrier 330 so that bubbles do not collect alonga second side 334 of anion permeable barrier 330.

Support member 350 is configured to direct flow F₁ of a first processingfluid laterally across first surface 332 of anion permeable barrier 330and vertically to processing zone 312. Support member 350 accordinglycontrols the flow F₁ of the first processing fluid in processing chamber310 to provide the desired mass transfer characteristics in processingzone 312. Support member 350 also shapes the electric field inprocessing chamber 310.

Counter electrode 360 is spaced apart from second surface 334 of anionpermeable barrier 330 such that a flow F₂ of the second processing fluidmoves regularly outward across second surface 334 of anion permeablebarrier 330 at a relatively high velocity. Flow F₂ of the secondprocessing fluid sweeps oxygen bubbles and/or particles from the anionpermeable barrier 330. Reactor 100 further includes flow restrictor 370around counter electrode 360. Flow restrictor 370 is a porous materialthat creates a back pressure in anode chamber 320 to provide a uniformflow between counter electrode 360 and second surface 334 of the anionpermeable barrier 330. As a result, the electric field can beconsistently maintained because flow restrictor 370 mitigates velocitygradients in the second processing fluid where bubbles and/or particlescan collect. The configuration of counter electrode 360 and flowrestrictor 370 also maintains a pressure in the anode chamber 320 duringplating that presses the anion permeable barrier 330 against supportmember 350 to impart the desired contour to anion permeable barrier 330.

Reactor 100 operates by positioning workpiece 344 in processing zone312, directing flow F₁ of the first processing fluid through processingchamber 310, and directing the flow F₂ of the second processing fluidthrough anode chamber 320. As the first and second processing fluidsflow through reactor 100, an electric potential is applied to workpiece344 via electrical contacts 342 and counter electrode 360 to establishan electric field in processing chamber 310 and anode chamber 320.

Another useful reactor for depositing metals using processes describedherein is described in U.S. Patent Application No. 2005/0087439, whichis expressly incorporated herein by reference.

While a preferred embodiment of the invention has been illustrated anddescribed, it will be appreciated that various changes can be madetherein without departing from the spirit and scope of the invention.

1. A process for electrolytically processing a microfeature workpiece as the working electrode with a first processing fluid and a counter electrode comprising: contacting a surface of the microfeature workpiece with the first processing fluid, the first processing fluid comprising first processing fluid species including a copper ion, an anion, and a complexing agent; contacting the counter electrode with a second processing fluid; producing an electrochemical reaction at the counter electrode; and substantially preventing movement of cationic species between the first processing fluid and the second processing fluid species.
 2. The process of claim 1, wherein the step of substantially preventing movement of cationic species between the first processing fluid and the second processing fluid comprises providing an anion permeable barrier between the first processing fluid and the second processing fluid.
 3. The process of claim 2, wherein the anion permeable barrier is an anion exchange membrane.
 4. The process of claim 1, wherein the working electrode is a cathode, and the counter electrode is an anode.
 5. The process of claim 4, further comprising the step of electrolytically depositing the copper ion onto the surface of the microfeature workpiece.
 6. The process of claim 5, wherein the first processing fluid further includes a counter anion of the copper ion and the process further comprises the step of passing the counter anion from the first processing fluid to the second processing fluid through the anion exchange membrane.
 7. The process of claim 4, wherein the anode is an inert anode.
 8. The process of claim 4, wherein the anode is a consumable anode.
 9. The process of claim 3, further comprising the step of passing the anion between the first processing fluid and the second processing fluid through the anion exchange membrane.
 10. The process of claim 1, wherein the first processing fluid has a pH greater than 7.0.
 11. The process of claim 1, further comprising the step of adding a copper ion to the first processing fluid.
 12. The process of claim 11, wherein the copper ion is added to the first processing fluid by adding a copper metal salt to the first processing fluid.
 13. The process of claim 1, wherein the first processing fluid species further include a pH adjustment agent and a buffer.
 14. The process of claim 13, further comprising the step of adding a pH adjustment agent to the second processing fluid.
 15. The process of claim 13, wherein the second processing fluid comprises a pH adjustment agent and a buffer.
 16. The process of claim 15, wherein buffer concentration in the first processing fluid is equal to or less than buffer concentration in the second processing fluid.
 17. The process of claim 1, wherein the concentration of the anion in the first processing fluid is greater than the concentration of the anion in the second processing fluid.
 18. The process of claim 1, wherein the complexing agent is selected from the group consisting of ethylene diamine, ethylene diamine tetraacetic acid and its salts, cyclam, porphrin, bipyridyl, pyrolle, thiophene, and polyamines.
 19. The process of claim 1, wherein the complexing agent is selected from compounds that contain a nitrogen-containing chelating group R—NR₂—R₁, where R is any alkyl or aromatic group and R₁ and R₂ are H, alkyl or aryl organic groups or polymer chains.
 20. The process of claim 1, wherein the complexing agent includes chemical compounds having at least one part with the chemical structure COOR₁—COHR₂R₃ where R₁ is an organic group covalently bound to the carboxylate group (COO), R₂ is either hydrogen or an organic group, and R₃ is either hydrogen or an organic group.
 21. The process of claim 20, wherein the complexing agent is selected from the group consisting of citric acid and salts thereof, tartaric acid and salts thereof, diethyltartrate, diisopropyltartrate, and dimethyltartrate.
 22. The process of claim 1, wherein pH of the first processing fluid is substantially equal to pH of the second processing fluid.
 23. The process of claim 4, wherein the surface of the microfeature workpiece onto which the copper ion is deposited comprises a seed material.
 24. The process of claim 4, wherein the surface of the microfeature workpiece onto which the copper ion is deposited comprises a barrier material.
 25. A process for electrolytically processing a microfeature workpiece with a first processing fluid and an inert anode comprising: contacting a surface of the microfeature workpiece with the first processing fluid, the first processing fluid including a copper ion to be deposited onto the surface of the microfeature workpiece, a counter anion to the copper ion, and a complexing agent; contacting the inert anode with a second processing fluid, an anion permeable barrier located between the first processing fluid and the second processing fluid; producing an oxidizing agent at the inert anode; adding a copper ion to the first processing fluid; passing the counter anion from first processing fluid to the second processing fluid through the anion permeable barrier; and depositing the copper ion in the first processing fluid onto the surface of the microelectronic workpiece.
 26. A process for electrolytically processing a microfeature workpiece with a first processing fluid and an inert anode comprising: contacting a surface of the microfeature workpiece with the first processing fluid, the first processing fluid comprising first processing fluid species including a copper ion to be deposited onto the surface of the microelectronic workpiece; and contacting the inert anode with a second processing fluid that includes a buffer and a pH adjustment agent, an ion permeable barrier located between the first processing fluid and the second processing fluid.
 27. The process of claim 29 wherein the buffer is boric acid.
 28. The process of claim 29 wherein the pH adjustment agent is tetramethylammonium hydroxide.
 29. A system for electrolytically processing a microfeature workpiece with a first processing fluid comprising: a chamber including: a processing unit for receiving the first processing fluid; a counter electrode unit for receiving a second processing fluid; an counter electrode in the counter electrode unit; an anion permeable barrier between the processing unit and the counter electrode unit; a source of complexing agent; a source of a copper ion in fluid communication with the processing unit; and a source of a pH adjustment agent in fluid communication with the counter electrode unit.
 30. The process of claim 1, wherein the counter electrode comprises multiple electrodes.
 31. The process of claim 1, wherein the working electrode comprises multiple electrodes.
 32. The process of claim 1, wherein the working electrode is an anode, and the counter electrode is a cathode.
 33. The process of claim 32, further comprising electrolytic dissolution of copper on the surface of the microfeature workpiece.
 34. The process of claim 32, wherein the cathode is an inert electrode in contact with the second processing fluid.
 35. The process of claim 34, wherein the second processing fluid includes an anion and a cation.
 36. The process of claim 35, wherein reduction of chemical species in the second processing fluid occurs at the cathode.
 37. The process of claim 36, wherein non-anionic chemical species in the first processing fluid are separated from the inert cathode by an anion permeable barrier.
 38. The process of claim 32, wherein the second processing fluid further includes a counter anion of copper present on the surface of the microfeature workpiece and the process further comprises passing the counter anion from the second processing fluid to the first processing fluid through an anion permeable barrier.
 39. The process of claim 32, wherein the first processing fluid has a pH less than 7.0.
 40. The process of claim 32, further comprising the step of adding an anion to the second processing fluid.
 41. The process of claim 40, wherein the anion is added to the second processing fluid by adding an acid to the second processing fluid.
 42. The process of claim 32, wherein the first processing fluid species further include a pH adjustment agent and a buffer.
 43. The process of claim 42, further comprising the step of adding a pH adjustment agent to the second processing fluid.
 44. The process of claim 42, wherein the second processing fluid comprises a pH adjustment agent and a buffer.
 45. The process of claim 44, wherein buffer concentration in the first processing fluid is equal to or greater than buffer concentration in the second processing fluid.
 46. The process of claim 1, wherein the copper ion is a cation of a copper salt and the anion is a counter ion of the copper ion of the copper salt, the second processing fluid comprising the anion, concentration of the anion in the second processing fluid being greater than concentration of the anion in the first processing fluid.
 47. The process of claim 1, further comprising the step of electrolytically dissolving metal from the surface of the microfeature workpiece.
 48. A process for electrolytically processing a microfeature workpiece with a first processing fluid and cathode comprising: contacting a surface of the microfeature workpiece with the first processing fluid, the first processing fluid including an anion; contacting the cathode with a second processing fluid containing the anion, an anion permeable barrier located between the first processing fluid and the second processing fluid; reducing chemical species in the second processing fluid; adding acid to the second processing fluid; passing the anion from the second processing fluid to the first processing fluid through the anion permeable barrier; and electrolytically dissolving copper from the surface of the microfeature workpiece.
 49. A system for electrolytically processing a microfeature workpiece with a first processing fluid comprising: a chamber including: a processing unit for receiving the first processing fluid; a counter electrode unit for receiving a second processing fluid; a cathode in the counter electrode unit; an anion permeable barrier between the processing unit and the counter electrode unit; a source of copper counter ion in fluid communication with the counter electrode unit; and a source of a pH adjustment agent in fluid communication with the processing unit. 